EP0866118A2 - Particule de détergent - Google Patents

Particule de détergent Download PDF

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Publication number
EP0866118A2
EP0866118A2 EP98200736A EP98200736A EP0866118A2 EP 0866118 A2 EP0866118 A2 EP 0866118A2 EP 98200736 A EP98200736 A EP 98200736A EP 98200736 A EP98200736 A EP 98200736A EP 0866118 A2 EP0866118 A2 EP 0866118A2
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EP
European Patent Office
Prior art keywords
acid
detergent
particle
alkyl
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98200736A
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German (de)
English (en)
Other versions
EP0866118A3 (fr
Inventor
Gerard Marcel Baillely
Stuart Clive Askew
Graham Alexander Sorrie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0866118A2 publication Critical patent/EP0866118A2/fr
Publication of EP0866118A3 publication Critical patent/EP0866118A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to an agglomerated or extruded detergent particle, comprising perborate bleach, an acid source and one or more surfactants, for use in detergent compositions which are suitable for use in laundry washing methods.
  • the invention also relates to a process for making the agglomerated or extruded detergent particle.
  • the (high density) detergents comprising high levels of bleach and surfactant can lead to poor solubility properties, arising from low rate of dissolution or the formation of gels, and thus to poor dispensing of the product, either from the dispensing drawer of a washing machine, or from a dosing device placed with the laundry inside the machine.
  • This poor dispensing is often caused by gelling of particles, which have high levels of surfactant and/ or bleach, upon contact with water.
  • the gel prevents a proportion of the detergent powder from being solubilized in the wash water which reduces the effectiveness of the powder. This is a particular problem at low water pressures and/or at lower washing temperature.
  • EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a detergent. Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the percarbonate bleach.
  • EP-A-0 639 639 contains a similar disclosure in this respect.
  • effervescence to improve the dispensability of granular materials has been used extensively in pharmaceutical preparations.
  • the use of this simple effervescent system has also been described for improving the dispersibility of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2,184,946.
  • EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of 350 to 150 microns.
  • US-A-5, 114,647 discloses a sanitising composition comprising granules of alkali metal carbonate and aliphatic carboxylic acid of a particle size of 150 to 2,000 microns.
  • EP-A-0 333 223 discloses a bathing preparation comprising fumaric acid having an average particle size of 50-500 microns.
  • an acid source is agglomerated with or extruded along with the surfactants, or a part thereof, and the perborate bleach to form an agglomerated or extruded detergent particle.
  • an alkali source should be present, capable of producing a gas when reaction with the acidic source.
  • the improved dispensing of the surfactant(s) and the perborate bleach can amount to an overall improved and more efficient performance.
  • an agglomerate or extruded detergent particle comprising a perborate component, one or more surfactants and an acid source.
  • other detergent ingredient can be present in the agglomerate or extrudate.
  • the agglomerated or extruded detergent particle can be included in detergents comprising an alkali source capable of reacting with the acid source to produce a gas.
  • a process for making the agglomerate or extruded detergent particle there is also provided.
  • the agglomerate or extruded detergent particle of the present invention contains one or more surfactants and an acid source and a perborate component, which are described below.
  • the amount of each component in the agglomerate or extruded detergent particle can vary depending on the application of the particle and on the nature of the final detergent composition comprising the particle. For example, when the particle will be used in a detergent composition comprising one or more of the same ingredients as the particle, the level thereof in the particle can be reduced.
  • the level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
  • the level of acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle
  • the level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
  • At least one anionic surfactant is present.
  • a nonionic surfactant and an anionic surfactant are present.
  • an anionic and a cationic and optionally a nonionic surfactant are present.
  • a cationic surfactant preferably a silicate or alumino silicate containing material is present.
  • magnesium sulphate is present in the particle, preferably at a level of from 0.1% to 8%, more preferably of from 0.2% to to 5%, most preferably from 0.3% to 3% by weight of the particle.
  • the particle does not comprise a bleach activator and/ or crystalline layered silicate.
  • the agglomerate or extruded particle can optionally comprise additional detergent ingredients.
  • Preferred optional ingredients in the particle can be builders (alumino silicates, polymeric carboxylates), an alkali source, bleach activators and bleach catalysts.
  • the level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle
  • the total level of surfactant in the detergent composition is preferably of from 1% to 90%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight of the detergent composition.
  • the surfactant in the agglomerate or extruded particle is selected from anionic, nonionic and cationic surfactants and mixtures thereof.
  • ampholytic, amphoteric and zwitterionic surfactants can be present in the particle.
  • the agglomerated or extruded detergent particle in accordance with the present invention preferably comprise one or more anionic surfactants.
  • anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono- di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate surfactants are preferred.
  • the level of anionic surfactant is preferably from 10% to 95%, more preferably from 20% to 60%, most preferably from 25% to 50% by weight of the particle.
  • the total level of anionic surfactant is preferably from 2% to 40%, more preferably from 4% to 30%, even more preferably from 5% to 25% most preferably from 6% to 15% by weight of the composition.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N-(C 1 -C 4 alkyl) and -N-(C 1 -C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 10 -C 18 alkyl sulfates, more preferably the C 11 -C 15 branched chain alkyl sulfates and the C 12 -C 14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 11 -C 18 , most preferably C 11 -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C 5 -C 20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C 6 -C 22 primary or secondary alkane sulfonates, C 6 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH 2 CH 2 0) x CH 2 C00 - M + wherein R is a C 6 to C 18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR 1 -CHR 2 -O)-R 3 wherein R is a C 6 to C 18 alkyl group, x is from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (R 1 ) CH 2 COOM, wherein R is a C 5 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion.
  • R is a C 5 -C 17 linear or branched alkyl or alkenyl group
  • R 1 is a C 1 -C 4 alkyl group
  • M is an alkali metal ion.
  • Another preferred surfactant of the invention is one or more cationic surfactants.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Another preferred cationic surfactant is an C 6 -C 18 alkyl or alkenyl ester of an quaternary ammonium alcohol, such as quaternary choline esters.
  • the level of cationic surfactant is preferably from 1% to 20%, more preferably from 9% to 15%, most preferably from 4% to 10% by weight of the particle.
  • the level of cationic surfactant is preferably from 0.2% to 20%, more preferably from 0.5% to 15%, even more preferably from 1% to 10%, most preferably from 1% to 5% by weight of the composition.
  • the detergent composition of the present invention preferably contains a nonionic surfactant. Essentially any nonionic surfactant can be used herein.
  • the level of nonionic surfactant is preferably from 5% to 60%, more preferably from 10% to 45%, most preferably from 15% to 35% by weight of the particle.
  • the level of nonionic surfactant is preferably from 1% to 30%, more preferably from 2% to 25%, even more preferably from 3% to 15%, most preferably from 4% to 12% by weight of the composition.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols nonionic ethoxylated/propoxylated fatty alcohols nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Nonionic polyhydroxy fatty acid amide surfactant Nonionic polyhydroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : R1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof preferable C1-C4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight-chain C 5 -C 19 alkyl or alkenyl, more preferably straight-chain C 9 -C 17 alkyl or alkenyl, most preferably straight-chain C 11 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R 6 CON(R 7 ) 2 wherein R 6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and -(C 2 H 4 O) x H, where x is in the range of from 1 to 3.
  • Suitable alkylpolysaccharides for use herein are disclosed in US. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula R 2 O(C n H 2n O)t(glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl. hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Optional amphoteric surfactants for use in the particle or detergent compositions, comprising the particle include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R 3 (OR 4 ) x N 0 (R 5 ) 2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C 10 -C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol. Inc., Dayton NJ.
  • zwitterionic surfactants can be incorporated into the particle or detergent compositions comprising the particle.
  • These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
  • Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R') 2 N + R 2 COO - wherein R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group.
  • Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • an acid source or source of acidity
  • the detergent composition contains an alkali source, capable of reacting with the acid source to produce a gas.
  • the alkali source or part thereof can be comprised in the particle.
  • the level of the acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle.
  • the level of the source of acidity is preferably present of from 0.1% to 50%, more preferably from 0. 5% to 25%, even more preferably from 1% to 12%, most preferably from 1% to 7% weight of the composition.
  • the acid source has a particle size in the range of from about 150 microns to about 710 microns, with at least about 37% by weight of the acid source having a particle size of about 350 microns or less. In a preferred embodiment 100% of the acid source has a particle size of about 710 microns or less Alternatively, greater than about 38%, more preferably 38.7%, of the particulate acid source has a particle size of about 350 microns or less.
  • the particle size of the acid source is calculated by sieving a sample of the source of acidity on a series of Tyler sieves. For example, a Tyler sieve mesh 100 corresponds to an aperture size of 150 microns. The weight fractions thereby obtained are plotted against the aperture size of the sieves.
  • the acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof or a mixture thereof.
  • the acid source may be a mono-, bi- or tri-protonic acid.
  • Preferred derivatives include a salt or ester of the acid.
  • the source of acidity is preferably non-hygroscopic, which can improve storage stability. However, monohydrates acids can also be useful herein. Organic acids and their derivatives are preferred.
  • the acid is preferably water-soluble. Suitable acids include citric, glutaric, succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof Citric acid is especially preferred.
  • Another essential ingredient of the agglomerate or extruded detergent particle of the present invention is a perborate component, which is capable of bleaching.
  • the level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
  • the perborate is preferably present at a level of from 1% to 40% by weight, more preferably from 6% to 25% by weight, most preferably from 13% to 20% by weight of the compositions.
  • the perborate is preferably in the form of a salt, normally in the form of the alkali metal, preferably sodium salt.
  • the perborate bleach is preferably sodium perborate in the form of the monohydrate or tetrahydrate, which can be represented respectively with the nominal formula NaBO 2 H 2 O 2 and NaBO 2 H 2 O 2 .3H 2 O.
  • the perborate bleach may be included as the crystalline solid without additional protection.
  • preferred executions of certain granular compositions utilize a coated form of the perborate bleach which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof or organic materials such as waxes, oils, or fatty soaps.
  • an alkali source is generally present in the detergent composition such that it has the capacity to react with the acid source to produce a gas.
  • this gas is carbon dioxide, and therefore the alkali is a carbonate, or a suitable derivative thereof.
  • the alkali source, or part thereof can he present in the particle.
  • the detergent composition comprising the particle of the present invention, preferably contains from about 2% to about 75%, preferably from about 5% to about 60%, most preferably from about 10% to about 30% by weight of the alkali source.
  • the agglomerate or extrudate preferably contains from about 5% to about 60%, more preferably from 10% to 50%, most preferably from 15% to 35% of the alkali source.
  • the alkali source is a carbonate.
  • preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No 2,321,001 published on November 15, 1973.
  • Alkali metal percarbonate salts may also be included in the detergent compositions and are also suitable sources of carbonate species and are described below in more detail.
  • the alkali source may also comprise other components, such as a silicate.
  • Suitable silicates include the water soluble sodium silicates with an SiO 2 : Na 2 O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred.
  • the silicates may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an SiO 2 : Na 2 O ratio of 2.0 is the most preferred silicate.
  • Alkali metal persilicates are also suitable sources of silicate herein.
  • the agglomerate detergent particle can be prepared via a process comprising the steps of:
  • such a process involves mixing a effective amount of powder, including the acid source, with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, preferably two, such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany.
  • a high shear mixer is used, such as a Lodige CB (Trade Name).
  • a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Name) ad a Lodige KM (Trade name) or Schugi KM (Trade Name).
  • a low shear mixer such as a Lodige CB (Trade Name) ad a Lodige KM (Trade name) or Schugi KM (Trade Name).
  • a low shear mixer such as a Lodige CB (Trade Name) ad a Lodige KM (Trade name) or Schugi KM (Trade Name).
  • the agglomerates are thereafter dried and/ or cooled.
  • An other agglomeration process involves mixing of various components of the final agglomrate in different stages, using an fluidised bed.
  • a preferred particle in accord with the present invention can be agglomerated by addition. preferably by spraying on, of nonionic, anionic surfactants and optionally a wax, or mixtures thereof to the acid source in powdered form and other optional ingredients. Then, additional components, including the perborate bleach and optinally the alkali source or part thereof can be added and agglomerated in one or more stages, thus forming the final agglomerate particle.
  • no bleach activator and/ or crystalline layered silicate is added to the agglomerate mix in the agglomeration process for making the particle of the invention.
  • the agglomerate particles may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • a preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resulting agglomerates within specified limits.
  • Typical particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 mm to 1.00 mm in diameter.
  • a high active surfactant paste comprising a mix of, typically, from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant, and optionally it can contain an appropriate acid source.
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • Such pastes and methods for making and processing such pastes is for example described in WO 93/03 128.
  • the detergent composition has a density of greater than about 600 g/l and is in the form of powder or a granulate.
  • Extruded particles can generally be prepared by mixing the various components, optionally addition of powdered components and/or slip additives, forcing the obtained mixture by pressure through the extruder holes or the required diameter or less, cutting of the extruded paste into extrudates (granules) of the required length and rounding the extrudates.
  • WO 91/13678 and WO 91/02047 describe such processes.
  • the extruded particles can be made as follows.
  • the detergent ingredients can be mixed into one paste.
  • the various detergent components are pre-mixed in different pastes, preferably two, whereby the acid source preferably is present in a different pre-mixed past than the alkali source if present in the particle, especially when the alkaline source is a carbonate or bicarbonate.
  • one pre-mixed paste comprises the perborate component and part of the surfactant, preferably the anionic surfactant if present, and additional components such as zeolite and cationic surfactant, and one pre-mixed paste comprises the acid source and part of the surfactant, preferably the nonionic surfactant.
  • the premixed pastes will then be mixed to form one paste.
  • water and additional detergent components such as slip additives, additional bleach, enzymes, optionally bleach activators, stabilisers and soap can be added to the pre-mixed paste or pastes or to the paste as a whole, simultaneously with or shortly after the mixing process has started.
  • the paste obtained is coated with a slip material prior to or simultaneously with the introduction of the paste in the extruder.
  • slip additives are those compounds which also have a secondary detergent function, such as certain anionic and nonionic surfactants, polymeric polycarboxylates, polyvinyl alcohols.
  • the paste or coated paste is then passed through the holes (of the extruder) of the required diameter or less, whereafter the extruded granules are cut in to granules of the required length (about 0.1 mm to 2.0 mm, preferably about 0.4 mm to 1.0 mm).
  • Typical particle diameter sizes are from 0.10 mm to 5.0 mm, preferably from 0.25 mm to 3.0mm, most preferably from 1.00 mm to 2.50.
  • the viscosity of the paste should be controlled to avoid cacking of the paste in the extruder or during mixing and to avoid the paste from blocking the extruder.
  • the viscosity is best controlled by heating and cooling the paste and/ or the extruder.
  • the obtained extrudates are rounded, to obtain round or spherical particles.
  • the thus obtained particles are dusted with a powder, preferably zeolite, and dried, to form equally shaped granules, and to avoid agglomeration of the granules.
  • a powder preferably zeolite
  • the agglomerate or extruded detergent particle and/ or the detergent compositions, comprising the particle of the invention may also contain additional ingredients or components.
  • additional ingredients and levels of incorporation thereof will depend on the physical form of the final composition, and the precise nature of the washing operation for which it is to be used.
  • the detergent particle preferably comprises as an additional ingredient one or more builders, preferably alumino silicates and/ or organic polycarboxylate polymers, alkali sources, bleach activators or bleach catalysts, or mixtures thereof.
  • the detergent compositions comprising the particle of the invention, preferably contain one or more additional detergent components selected from surfactants as described above, additional acid sources, additional bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • the particle and/ or the detergent compositions of the present invention can contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the particle and/ or the detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in the detergent composition at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • the partially soluble or insoluble builder compound is preferably present at a level of from 5% to 85% by weight, preferably from 15% to 60% by weight, most preferably from 20% to 50% weight of the particle.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) z (SiO 2 )y]. xH 2 O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can he naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [AlO 2 ) 12 (SiO 2 ) 12 ]. xH 2 O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ]. 276 H 2 O.
  • the particle of the invention does not comprise a crystalline layered silicate.
  • preferred crystalline layered silicates for use in the detegrent compositions herein have the general formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is ⁇ -Na 2 Si 2 0 5 , available from Hoechst AG as NaSKS-6.
  • metal percarbonates particularly sodium percarbonate is an optional perhydrate which can be incorporated into the particle or detergent composition of the invention.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na 2 CO 3 .3H 2 O 2 , and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • a preferred feature of detergent compositions of the invention is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of: and mixtures thereof wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms.
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms,
  • R 4 is H or R 3 , and
  • Y is H or a solubilizing group. Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
  • the preferred solubilizing groups are -SO 3 - M + , -CO 2 - M + , -SO 4 - M + , -N - (R 3 ) 4 X - and O ⁇ --N(R 3 ) 3 and most preferably -SO 3 - M + and -CO 2 - M + wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
  • Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: wherein R 1 is an alkyl group with from 1 to 14 carbon atoms, R 2 is an alkylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K 1,382,594; EP 475,512, 458,396 and 284,292; and JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein R 1 is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: wherein R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • the particle and/ or the compositions optionally contain a transition metal containing bleach catalyst.
  • a transition metal containing bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • Such catalysts are disclosed in U.S. Pat. 4,430,243.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclonane) 2 -(ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 -(ClO 4 ) 2 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 3 , and mixtures thereof.
  • ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazyaclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
  • bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH 3 ) 3- (PF 6 ).
  • Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands including N 4 Mn III (u-O) 2 Mn IV N 4 ) + and [Bipy 2 Mn III (u-O) 2 Mn IV bipy 2 ]-(ClO 4 ) 3 .
  • bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
  • the particle and or the detergent compositions, comprising the particle of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • Another preferred ingredient useful in the detergent compositions, comprising the particle is one or more additional enzymes.
  • the enzymes or part thereof cam be present in the agglomerated or ended particle of the invention.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens . Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes , which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza , as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414 Huge-Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred additional components of the particle and/ or the detergent compositions, comprising the particle in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Another organic compound which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, C 1 -C 4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof a is from 0 to 20, preferably from 0 to 4 (e.g.
  • the detergent compositions when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g. stearone)-N-alkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the particle and/ or the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • the particle but preferably the detergent compositions may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone ad N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula: wherein P is a polymerisable unit, and A is -O-, -S-, -N-; x is O or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures : wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially valuable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvinylmidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R 1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Cationic fabric softening agents can also be incorporated into the particle and/or the compositions.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
  • compositions suitable for inclusion in the particle and the detergent compositions include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • the final detergent compositions preferably have a pH measured as a 1% solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0.
  • the particles may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • the most preferred way to process the particles, as described above, is by agglomerating or mixing and extruding powders (e.g. aluminosilicate, optionally carbonate) with high active surfactant pastes and to control the particle size of the resultant particles within specified limits.
  • compositions comprising the particle
  • the compositions can be of the form of the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the mean particle size of the base composition of granular compositions in accordance with the invention can be from 0.1 mm to 5.0 mm, but it should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular detergent compositions is typically of at least 500 g/litre, more preferably from 650 g/litre to 1200 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • a dispensing device is employed in the washing method.
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
  • the dispensing device containing the detergent product is placed inside the drum.
  • water is introduced into the drum and the drum periodically rotates.
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
  • the device may possess a number of openings through which the product may pass.
  • the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.
  • An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette”.
  • Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
  • Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070.
  • the latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium.
  • the support ring is provided with a masking arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration or a similar structure in which the walls have a helical form.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP98200736A 1997-03-20 1998-03-09 Particule de détergent Withdrawn EP0866118A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9705840 1997-03-20
GB9705840A GB2323384A (en) 1997-03-20 1997-03-20 A detergent composition

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EP0866118A2 true EP0866118A2 (fr) 1998-09-23
EP0866118A3 EP0866118A3 (fr) 1998-12-16

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000024859A1 (fr) * 1998-10-26 2000-05-04 The Procter & Gamble Company Particules detergentes et leurs procedes de fabrication
EP1004658A2 (fr) * 1998-11-24 2000-05-31 Henkel Kommanditgesellschaft auf Aktien Agent de lavage comprenant de l'acide citrique
EP1048712A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé pour le traitement de textiles en utilisant un additif pour la lessive en forme de comprimés
EP1048714A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé de distribution d'une composition détergente
EP1048715A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé de distribution d'une composition détergente
US6491947B2 (en) 2000-11-03 2002-12-10 Chemlink Laboratories, Llc Expanded perborate salt, use, and method of production
WO2003044154A1 (fr) * 2001-11-16 2003-05-30 Colgate-Palmolive Company Systeme de nettoyage comprenant une poudre de nettoyage disposee dans une enveloppe hydrosoluble
EP1633847A2 (fr) * 2003-05-30 2006-03-15 Orange Glo International, Inc. Preparations detergentes contenant des sels alcalins de peroxyde et des acides organiques
WO2009122125A1 (fr) * 2008-04-01 2009-10-08 Reckitt Benckiser Inc. Compositions de traitement du linge
EP2129762B2 (fr) † 2007-02-20 2015-10-07 Henkel AG & Co. KGaA Complexes métalliques sidérophores utilisés comme catalyseurs de blanchiment

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252664A (en) * 1978-10-30 1981-02-24 Colgate-Palmolive Company Effervescent granules
EP0296813A1 (fr) * 1987-06-24 1988-12-28 Imperial Chemical Industries Plc Compositions de poudre et compositions détergentes
EP0483413A1 (fr) * 1990-10-30 1992-05-06 The Procter & Gamble Company Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide
WO1992018596A1 (fr) * 1991-04-19 1992-10-29 The Procter & Gamble Company Compositions detersives granulaires pour lessive, presentant une solubilite amelioree
EP0534525A2 (fr) * 1991-09-27 1993-03-31 Unilever N.V. Poudres détergentes et leur procédé de préparation
WO1994003568A1 (fr) * 1992-08-01 1994-02-17 The Procter & Gamble Company Compositions detersives a faible niveau de gelification et procede de preparation
WO1995027774A1 (fr) * 1994-04-07 1995-10-19 The Procter & Gamble Company Composition de blanchiment comprenant un catalyseur de blanchiment contenant un metal et des antioxydants
WO1996029389A1 (fr) * 1995-03-17 1996-09-26 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication d'un detergent ou nettoyant en poudre
WO1998004662A1 (fr) * 1996-07-31 1998-02-05 The Procter & Gamble Company Composition de detergence comprenant une source acide presentant une dimension de particule specifique
WO1998004668A1 (fr) * 1996-07-31 1998-02-05 The Procter & Gamble Company Composition detergente

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4540504A (en) * 1983-04-22 1985-09-10 Warner-Lambert Company Denture cleaner having improved dissolution time and clarity and method of preparation
JPS63199796A (ja) * 1987-02-16 1988-08-18 花王株式会社 高密度粒状洗剤組成物

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252664A (en) * 1978-10-30 1981-02-24 Colgate-Palmolive Company Effervescent granules
EP0296813A1 (fr) * 1987-06-24 1988-12-28 Imperial Chemical Industries Plc Compositions de poudre et compositions détergentes
EP0483413A1 (fr) * 1990-10-30 1992-05-06 The Procter & Gamble Company Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide
WO1992018596A1 (fr) * 1991-04-19 1992-10-29 The Procter & Gamble Company Compositions detersives granulaires pour lessive, presentant une solubilite amelioree
EP0534525A2 (fr) * 1991-09-27 1993-03-31 Unilever N.V. Poudres détergentes et leur procédé de préparation
WO1994003568A1 (fr) * 1992-08-01 1994-02-17 The Procter & Gamble Company Compositions detersives a faible niveau de gelification et procede de preparation
WO1995027774A1 (fr) * 1994-04-07 1995-10-19 The Procter & Gamble Company Composition de blanchiment comprenant un catalyseur de blanchiment contenant un metal et des antioxydants
WO1996029389A1 (fr) * 1995-03-17 1996-09-26 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication d'un detergent ou nettoyant en poudre
WO1998004662A1 (fr) * 1996-07-31 1998-02-05 The Procter & Gamble Company Composition de detergence comprenant une source acide presentant une dimension de particule specifique
WO1998004668A1 (fr) * 1996-07-31 1998-02-05 The Procter & Gamble Company Composition detergente

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 8839 Derwent Publications Ltd., London, GB; Class A97, AN 88-274331 XP002080535 & JP 63 199796 A (KAO CORP) , 18 August 1988 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000024859A1 (fr) * 1998-10-26 2000-05-04 The Procter & Gamble Company Particules detergentes et leurs procedes de fabrication
EP1004658A2 (fr) * 1998-11-24 2000-05-31 Henkel Kommanditgesellschaft auf Aktien Agent de lavage comprenant de l'acide citrique
EP1004658A3 (fr) * 1998-11-24 2000-08-09 Henkel Kommanditgesellschaft auf Aktien Agent de lavage comprenant de l'acide citrique
WO2000066687A1 (fr) * 1999-04-30 2000-11-09 The Procter & Gamble Company Procede de traitement de tissus au moyen d'un comprime d'additif detergent a lessive
EP1048714A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé de distribution d'une composition détergente
EP1048715A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé de distribution d'une composition détergente
EP1048712A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé pour le traitement de textiles en utilisant un additif pour la lessive en forme de comprimés
WO2000066689A1 (fr) * 1999-04-30 2000-11-09 The Procter & Gamble Company Procede de liberation d'une composition detergente
WO2000066691A1 (fr) * 1999-04-30 2000-11-09 The Procter & Gamble Company Procede de distribution d'une composition de detergent
US6491947B2 (en) 2000-11-03 2002-12-10 Chemlink Laboratories, Llc Expanded perborate salt, use, and method of production
WO2003044154A1 (fr) * 2001-11-16 2003-05-30 Colgate-Palmolive Company Systeme de nettoyage comprenant une poudre de nettoyage disposee dans une enveloppe hydrosoluble
EP1633847A2 (fr) * 2003-05-30 2006-03-15 Orange Glo International, Inc. Preparations detergentes contenant des sels alcalins de peroxyde et des acides organiques
EP1633847A4 (fr) * 2003-05-30 2007-04-11 Church & Dwight Co Inc Preparations detergentes contenant des sels alcalins de peroxyde et des acides organiques
EP2129762B2 (fr) † 2007-02-20 2015-10-07 Henkel AG & Co. KGaA Complexes métalliques sidérophores utilisés comme catalyseurs de blanchiment
WO2009122125A1 (fr) * 2008-04-01 2009-10-08 Reckitt Benckiser Inc. Compositions de traitement du linge

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GB2323384A (en) 1998-09-23
GB9705840D0 (en) 1997-05-07
EP0866118A3 (fr) 1998-12-16
CA2232205A1 (fr) 1998-09-20

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